BENZENE AND AROMATIC COMPOUNDS

Aromatic compounds :

benzene and derivatives of benzene 1866 - Friedrich Kekule proposed benzene as a cyclic structure with three double bonds (localized double bond)

in equilibrium

 The true structure of benzene can be explained by the concept of resonance and electron delocalization due to orbital overlap.

Structure of Benzene

O Each sp2 hybridized C in the ring has an unhybridized

p orbital perpendicular to the ring which overlaps around the ring. O The six pi electrons are delocalized over the six carbons.

The structure of benzene

degree of unsaturation It is planar All C-C bond lengths are equal The reaction is substitution not an addition
Br2 CCl4 Br Br (an addition reaction)

Br2 CCl4

Br

No reaction
Br
Br + HBr (substitution)

Br2 FeBr3

The heat of hydrogenation

H2

catalyst

H= 120 kj/mol

H2

catalyst

H= 240 kj/mol

H2

catalyst

H= 232 kj/mol

H2

catalyst

H= 208 kj/mol

Molar Heats of Hydrogenation

 Resonance energy is the extra stabilization

provided by the delocalization of the electrons in the aromatic compound.

Aromatic compounds tend to undergo

substitution rather than addition reaction, to retain their resonance energy. This behavior is characteristic of aromatic compounds.

Can we predict which compound is aromatic?

Aromatic Character : The (4n+2) Rule The criteria for aromatic character (aromaticity)
1. 2. 3.

4.

A molecule must be cyclic. A molecule must be planar. A molecule must be conjugated (uninterrupted) (p orbital on every atom) A molecule must satisfy Huckels rule : (4n+2) n = an integer, 0, 1,2, 3 and so on).

All compounds can be classified in one of three ways :

Aromatic: a cyclic, planar, completely conjugated compound with 4n+2 electrons Antiaromatic: a cyclic, planar, completely conjugated compound with 4n electrons

2.

3.

Not aromatic (or nonaromatic): a compound that lacks one (or more) of the following requirements for aromaticity ; being cyclic, planar and completely conjugated.

Example of aromatic compounds (4n+2) electrons

Structure and Name

10
N quinoline

naphthalene

14

anthracene

phenanthrene

Tropylium ion (6 electrons) 4n+2 = 6 n =1

aromatic

..

Cyclopentadienyl anion 6 electrons contain 4n+2 electrons

aromatic

antiaromatic

non aromatic

Activity
Which of the following compounds are aromatic? For any compound that is not aromatic, state why this is so.

a.
O

b.

H N

c.

Common Names of Benzene Derivatives

Phenol

Toluene

Aniline
O OH

Anisole
H 2C H

CH3

Benzaldehyde Acetophenone

Benzoic acid

Styrene

*Please memorize them

O Monosubstituted benzenes:

Nomenclature of Benzene Derivatives

ethylbenzene

tert-butylbenzene

Cl

chlorobenzene

O Disubstituted benzenes :
Common Name
Br Br

IUPAC Name

o-dibromobenzene

1,2-dibromobenzene

Br

m-dibromobenzene
Br

1,3-dibromobenzene

Br

Br

p-dibromobenzene

1,4-dibromobenzene

O If the two groups are different, alphabetize the

the name of the substituents:

Common name : o-bromochlorobenzene IUPAC name : 1-bromo-2-chlorobenzene

Common name : m-fluoronitrobenzene IUPAC name : 1-fluoro-3-nitrobenzene

NO2

O If one of the substituents is part of a common

root, use a common root name:

Common name : p-bromotoluene IUPAC name : 4-bromotoluene

Br
OH

Common name : o-nitrophenol IUPAC name : 2-nitrophenol

NO2

Polysubstituted benzenes: 3 substituent

Number to give the lowest possible numbers Alphabetize the substituent names. When substituents are part of common roots, the common root is located at C1.
NH2

CH2CH3 Cl CH2CH2CH3

Cl Cl

4-chloro-1-ethyl-2-propylbenzene

2,5-dichloroaniline

Aromatic rings as substituent: Phenyl group

CH3 CHCH2CH3

2-phenylbutane

O Benzyl group
H C H

C6H5CH2-

PhCH2

CH2Cl

benzyl chloride

Activity

Draw the structure of each compounds.

a. Ethylbenzene

b. p-xylene
c. diphenylmethane

a. Reactions of benzene b. Reactions involve monosubstitute of benzene c. Reactions involve polysubstitute of benzene d. Side-chain reactions of aromatic compounds

a. Reactions of benzene
Electrophilic Aromatic Substitution
Electrophile substitutes for a hydrogen on the benzene ring

General Mechanism

Energy Diagram for Bromination

1) Bromination of Benzene
Requires a stronger electrophile than Br2. Use a strong Lewis acid catalyst, FeBr3.

Chlorination and Iodination

Iodination requires an acidic oxidizing agent, like nitric acid, which oxidizes the iodine to an iodonium ion.

2) Nitration of Benzene
Use sulfuric acid with nitric acid to form the nitronium ion electrophile.

3) Sulfonation
Sulfur trioxide, SO3, in fuming sulfuric acid is the electrophile.

4) Friedel-Crafts Alkylation
Synthesis of alkyl benzenes from alkyl halides and a Lewis acid, usually AlCl3. Reactions of alkyl halide with Lewis acid produces a carbocation which is the electrophile.

Mechanism of Friedel-Crafts Alkylation

5) Friedel-Crafts Acylation

Acyl chloride is used in place of alkyl chloride. The acylium ion intermediate is resonance stabilized and does not rearrange like a carbocation. The product is a phenyl ketone that is less reactive than benzene.

Mechanism of Friedel-Crafts Acylation

Substitution Effects on Reactivity

Decreasing order of reactivity

W = withdraws electron from the ring (decrease electron density of the ring) the thus deactivating it (reacts slower than benzene)

What makes a substituent on a benzene ring electron donating or withdrawing electron.

effects. Then consider the net balance of both the inductive and the resonance effects.

R donates electrons by an inductive effects R has no resonance effects So R as an electron-donating group

opposing effects Z
inductively withdraw electron density

.. Z
donate electron density by resonance

Z = N, O, X If Z= N, O ; the resonance effect dominates and the net effect is electron donation If Z= X ; the inductive effect dominates and the net effect is electron withdrawing

Most activating (Rx go fastest)

-NH2 -NHR -NR2 -OH -OR

Strongly activating

Moderately activating

Weakly activating

Least activating

Deactivating substituents
F Cl

Least deactivating

Br I

Weakly deactivating

O -CH O -CR O -COR O -COH O -CCl

Moderately deactivating

Strongly deactivating

Most deactivating

Arrange the following terms of compounds in decreasing order of reactivity toward nitration
Br a) SO3H H OH CH3

COOH b)

OH

OCH3

CH3

Cl

H c)

NO2

NHCH3

OCH2CH3

Cl d)

COOH

NHCH3

OCH2CH3

CH3

NO2

Disubstituted Benzenes : Orientation

1) ortho , para director

2) meta director
Y G G Y

Classification of Substituents

To understand why a substituent direct an incoming electrophile to a particular position, we must look at the stability of the carbocation intermediate that is formed in the rate determining step.
Three different carbocation intermediates can be formed: O ortho-substituted carbocation; meta-substituted carbocation; para-substituted carbocation. The more stable the carbocation the more likely it is that it will formed.

Complete octet

Effects of Multiple Substituents on Electrophilic Aromatic Substitution

activating group and a deactivating group, the activating group usually directs the substitution.

O Strong ortho/para directors> moderate

ortho/para directors> all meta directors

Side-chain Reactions of Aromatic Compounds

Halogenation of an alkyl side chain

CH2CH2Cl

2. Oxidation of an alkyl side chain

Clemmensen Reduction
Acylbenzenes can be converted to alkylbenzenes by treatment with aqueous HCl and amalgamated zinc.

Synthesis of Benzenes Derivatives

O When designing a synthesis of substituted

benzenes, the order in which the substituent are introduced is crucial.

Example: Synthesize ortho-, meta-, and para-nitrobenzoic from toluene.

CO2H

CO2H NO2

CO2H

?????

toluene

NO2 NO2